US2656395A - Preparation of nitroolefins - Google Patents

Preparation of nitroolefins Download PDF

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US2656395A
US2656395A US2656395DA US2656395A US 2656395 A US2656395 A US 2656395A US 2656395D A US2656395D A US 2656395DA US 2656395 A US2656395 A US 2656395A
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nitric oxide
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings

Definitions

  • This invention relates to nitrooleflns and to methods for their preparation.
  • ..Nitroolefins are an important .class. of chemical intermediates .ior conversion to amines, amino- ;alcohols, ethers, thioethers etc.
  • preparation nitroolefins, .an me. in and nitric oxide havebeenreactedatessentially room temperature and atmospheric pressureinthe presenceof ultraviolet light to initiate the reaction-(J Chem...Soc. 19.44, 120).
  • the reaction .isnot clean cut and the yields ,of desired en'i'troolefln are poor.
  • v object of .the present invention is an "improved method for .the preparation of nitroolflfins.
  • a further object is such a method characterized bysubstantial yields and increased efficiency.
  • Other objects will be understood ,from .theiollowing detailed description of the inven- .tion.
  • the present invention is ,a process for the preparation of a nitroolefin which comprises reacting .with nitric oxide an olefin containing more than two carbon ,atoms ,;said reaction j'being conducted in anacidiomedium'in .th'e absence of air .atternperatures of Q80to 15.0" .C. and underpres- .sure'of'50 to .400 pounds per square 1 inch.
  • a pressure reactor is charged with a.s olution of the olefin in anhydrous acetic .acid, the :reactor is purged with -'oxygensfree nitrogen, and then the'jlatter is 're .moved by vacuum means. "The reactor .is then pressured with nitric oxide to ,a predetermined desired pressure, and thepressure 'maintainedhy lperiodic injections of nitric oxide. These conditions aremaintained until the press'uredropin five minutes is less than 20 pounds persquare inch. The contents are thenheated tobetween "80 andlf50 C. for oneto four hours. Thereafter, the reaction mixture is permitted to coolto room temperature and'the reactor discharged. The product isthen distilled under reduced pressure to recover-the desired nitroolefin.
  • the product was a *light yellow liquid which was insoluble in 2% aqueous sodium hydroxide. when the ;p-roduct was mixed withalcoholic hydrogen chloride, a blue color developed, which --wasi-ndicative of the presence-of a l-nitro group.
  • Example L was repe'atedwitha charge consistingof 30cc. of cyclohexene and 00. oflaoetic acid.
  • the charge was heated :at 100- CL with nitric oxide for 5 hours, during which itime the pressure was maintained at 100 ipoundszper square inch.
  • 'During thls time:therewas anachserved pressure drop corresponding -'to-0.'4 mole
  • the reactor was allowed to .0001,
  • Example III A pressure reactor was charged with 25 cc. of styrene in 100 cc. of acetic anhydride. The reactor was flushed with oxygen-free nitrogen and then evacuated. Nitric oxide was then admitted into the reactor to a pressure of 50 pounds per square inch and the mixture heated to 100 C. These conditions were maintained for 6.5 hours, during which time the pressure was maintained at the indicated level by periodic repressuring with nitric oxide. During this reaction period a pressure drop corresponded to 0.95 mole nitric oxide was noted. The reactor was allowed to cool, vented, and the contents discharged. The product was a red liquid containing some solid and it weighed 123 grams. Distillation through a 4" Vigreux column yielded 8.7 grams of a product, B. P. 101-111 C./1.0-1.5 mm., identified as omega-nitrostyrene. The yield was 27%.
  • the nitrosation of the olefins with nitric oxide may be carried out at temperatures in the range of 80 to 150 C. Best results, however, are realized within the more restricted range of 90 to 125 C. and this embraces the temperature conditions which are generally used.
  • the nitrosation reaction of this invention is carried out in an acidic medium and this is critical for operability.
  • this is critical for operability.
  • the process of Example II is repeated using chloroform or benzene as the medium in place of acetic acid, little or no reaction occurs.
  • replacing the acetic anhydride in the process of Examples I or III With chloroform, benzene, or other nonacidic reaction medium results in little or no reaction occurring.
  • Acetic acid and acetic anhydride are the preferred reaction media because they are abundantly available, relatively low in cost, easily removed from the reaction product, and have general good solvency characteristics.
  • acetic acid or anhydride other saturated aliphatic carboxylic acids and anhydrides may be used. Examples are propionic, butyric, etc., acids and anhydrides.
  • reaction medium used is not critical and it can be Varied over wide limits. For practical reasons, an amount is used to give solutions varying in concentration from to limits though without serious sacrifice in the efficiency of the process.
  • the nitric oxide used in the process of this invention should be of a high degree of purity. That is, it should not contain any sensible amounts of other oxides of nitrogen in order to 60% by volume. Deviation can be had from these hexene and styrene. It is to be understood, however, that it is applicable to the nitrosation of any olefin hydrocarbon containing more than two carbon atoms.
  • olefin hydrocarbons in addition to those of the examples, are propylene, butylene, octenes, dodecenes, octadecenes, methyl cyclohexene a-methyl styrene, butadiene, and isoprene.
  • the monoolefin hydrocarbons are preferred because they readily nitrosate with minimum of complicating side reaction product formation.
  • olefin is selected from the group consisting of propylene, butylene, octenes, dodecenes, octadecenes, cyclohexene, methyl cyclohexene, styrene, a-methyl styrene, butadiene and isoprene.
  • omeganitrostyrene which comprises reacting styrene and nitric oxide in the presence of acetic anhydride, in the absence of air, at temperatures between 90 and 125 C. and at a pressure from 50 to 400 pounds per square'inch.

Description

Patented Oct. 20, 1953 PREPARATION OF NITROOLEFINS .Bichard' EdwardlBenson, Claymong DeL assignor to E. I. du Pont de Nemours .and Company, Wilmington, -Del. a corporation of Delaware No Drawing. Application June'fi, I951,
Serial No. 23.0.1680
"'7 Claims.
This invention relates to nitrooleflns and to methods for their preparation.
..Nitroolefins are an important .class. of chemical intermediates .ior conversion to amines, amino- ;alcohols, ethers, thioethers etc. In one method .hitherto used for ,preparing nitroolefins, .an me. in and nitric oxide havebeenreactedatessentially room temperature and atmospheric pressureinthe presenceof ultraviolet light to initiate the reaction-(J Chem...Soc. 19.44, 120). The reaction .isnot clean cut and the yields ,of desired en'i'troolefln are poor. jE-lod and Nedelman, C. A. .21, 325411927) reacted nitric oxide withet ylene at 900" .C. and obtained hydrogen cyanide-along witha heavycarbondeposit and alarge amount of polymeric substances. Their results indicated .that .formationof .carbon and polymers might be avoidedby using lower temperature but this resulted' in a lowered yield of hydrogen cyanide.
v object of .the present invention is an "improved method for .the preparation of nitroolflfins. A further object issuch a method characterized bysubstantial yields and increased efficiency. Other objects will be understood ,from .theiollowing detailed description of the inven- .tion.
The present invention .is ,a process for the preparation of a nitroolefin which comprises reacting .with nitric oxide an olefin containing more than two carbon ,atoms ,;said reaction j'being conducted in anacidiomedium'in .th'e absence of air .atternperatures of Q80to 15.0" .C. and underpres- .sure'of'50 to .400 pounds per square 1 inch.
In one preferred aspect for operating the process of this invention, a pressure reactor is charged with a.s olution of the olefin in anhydrous acetic .acid, the :reactor is purged with -'oxygensfree nitrogen, and then the'jlatter is 're .moved by vacuum means. "The reactor .is then pressured with nitric oxide to ,a predetermined desired pressure, and thepressure 'maintainedhy lperiodic injections of nitric oxide. These conditions aremaintained until the press'uredropin five minutes is less than 20 pounds persquare inch. The contents are thenheated tobetween "80 andlf50 C. for oneto four hours. Thereafter, the reaction mixture is permitted to coolto room temperature and'the reactor discharged. The product isthen distilled under reduced pressure to recover-the desired nitroolefin.
The examples 'Lu'zhich .followeressubmitted to illustrate and not to limit the invention.
Example I A solution of 40.5 g. of cyclohexene in 100 cc. of acetic anhydride was "placed "in a pressure weasel, the vessel purged .with oxygen-tree rnitrogem-and ithen. evacuated briefly. The ;reactor .was then pressured to 200 pounds .per square inch nitric oxide. routed, and the contentsdischarged. Themeaction product was distilled :through a A 'Nigreux column. There werecollected 4E2 grams =oftyellow :oil, :B. P. "50163/D;4.-;0.8 mmncharacterized byaievelopment of;.bluezcolonuponladditional ialooh lic hydrogen chloride il-nitrocyclohexene.
tions collected were as follows:
:Fraction B.,P., C gfif Amount. :Remarks 1 25-50 15-16 90 cc; Mainly acetic an-- zye ide. 2 25-,-5 8. .V, 2 15.3 g Yellow oil. 3 Residue 27.0 g.. viscgusydarkpliar Fraction? was'combined'with the=simil ar iraotion from another run and-the combined material redistilled through a 4" Vig-reux column. The fractions collected were as -follows: I v
- B. P., Pressure Wei ht Fractlon O. mm. Gra ms *Remam Fraction 4 analyzes 56.82, 56;-8-'7"% carbon, 7446, 7.41% hydrogen, and 10.40, 10.58% -nitrogen.
The calculated values for CI-I9NO2 are 56:687.;
carbon, 7.14% hydrogen, and 11.02% nitrogen.
" The product was a *light yellow liquid which was insoluble in 2% aqueous sodium hydroxide. when the ;p-roduct was mixed withalcoholic hydrogen chloride, a blue color developed, which --wasi-ndicative of the presence-of a l-nitro group.
'The ultraviolet -spectrum of this product-was similar tothat reported for lnitrocyclohexene.
E mample II Example Lwas repe'atedwitha charge consistingof 30cc. of cyclohexene and 00. oflaoetic acid. The charge was heated :at 100- CL with nitric oxide for 5 hours, during which itime the pressure was maintained at 100 ipoundszper square inch. 'During thls time:therewas anachserved pressure drop corresponding -'to-0.'4 =mole The reactor was allowed to .0001,
3 Example III A pressure reactor was charged with 25 cc. of styrene in 100 cc. of acetic anhydride. The reactor was flushed with oxygen-free nitrogen and then evacuated. Nitric oxide was then admitted into the reactor to a pressure of 50 pounds per square inch and the mixture heated to 100 C. These conditions were maintained for 6.5 hours, during which time the pressure was maintained at the indicated level by periodic repressuring with nitric oxide. During this reaction period a pressure drop corresponded to 0.95 mole nitric oxide was noted. The reactor was allowed to cool, vented, and the contents discharged. The product was a red liquid containing some solid and it weighed 123 grams. Distillation through a 4" Vigreux column yielded 8.7 grams of a product, B. P. 101-111 C./1.0-1.5 mm., identified as omega-nitrostyrene. The yield was 27%.
The examples have illustrated certain preferred embodiments. It is to be understood that departure may be had from these without digressing from the scope and spirit of this invention.
The nitrosation of the olefins with nitric oxide may be carried out at temperatures in the range of 80 to 150 C. Best results, however, are realized within the more restricted range of 90 to 125 C. and this embraces the temperature conditions which are generally used.
In practice it is convenient to charge the reactor with the olefin and an acidic solvent and then to inject nitric oxide to a predetermined pressure. The reaction mixture is then heated to the temperature selected for reaction and the pressure within the system maintained by peri odic injections of nitric oxide. As a rule, the pressures used will range from 50 to 400 pounds per square inch. If desired, however, the process can be carried out at atmospheric pressure but the yield of desired nitroolefins is markedly decreased.
The nitrosation reaction of this invention is carried out in an acidic medium and this is critical for operability. Thus, if the process of Example II is repeated using chloroform or benzene as the medium in place of acetic acid, little or no reaction occurs. Likewise, replacing the acetic anhydride in the process of Examples I or III With chloroform, benzene, or other nonacidic reaction medium results in little or no reaction occurring.
Acetic acid and acetic anhydride are the preferred reaction media because they are abundantly available, relatively low in cost, easily removed from the reaction product, and have general good solvency characteristics. In place of acetic acid or anhydride, other saturated aliphatic carboxylic acids and anhydrides may be used. Examples are propionic, butyric, etc., acids and anhydrides.
The amount of reaction medium used is not critical and it can be Varied over wide limits. For practical reasons, an amount is used to give solutions varying in concentration from to limits though without serious sacrifice in the efficiency of the process.
The nitric oxide used in the process of this invention should be of a high degree of purity. That is, it should not contain any sensible amounts of other oxides of nitrogen in order to 60% by volume. Deviation can be had from these hexene and styrene. It is to be understood, however, that it is applicable to the nitrosation of any olefin hydrocarbon containing more than two carbon atoms. Examples of olefin hydrocarbons, in addition to those of the examples, are propylene, butylene, octenes, dodecenes, octadecenes, methyl cyclohexene a-methyl styrene, butadiene, and isoprene. The monoolefin hydrocarbons are preferred because they readily nitrosate with minimum of complicating side reaction product formation.
The process of this invention makes nitroolefins readily accessible. These compounds are attractive intermediates for amines, aminoalcohols, ethers, thioethers, and the like.
I intend to be limited only by the following patent claims:
I claim:
1. The process for the preparation of a nitroolefin which comprises reacting with nitric oxide an olefin containing more than two carbon atoms, said reaction being conducted in an acid medium in the absence of air at temperatures from to 150 C. and under pressure of 50 to 400 pounds per square inch.
2. The process for the preparation of a nitroolefin which comprises reacting with nitric oxide an olefin containing more than two carbon atoms, said reaction being conducted in the presence of a saturated aliphatic carboxylic acid anhydride in the absence of air at temperatures from 80 to 150 C. and under pressure of 50 to 400 pounds per square inch. 7
3. The process of claim 1 wherein the olefin is selected from the group consisting of propylene, butylene, octenes, dodecenes, octadecenes, cyclohexene, methyl cyclohexene, styrene, a-methyl styrene, butadiene and isoprene.
4. The process for the preparation of a nitroolefin which comprises reacting with nitric oxide an olefin'containing more than two carbon atoms, said reaction being conducted in an acid medium in the absence of air at temperatures from to C. and under pressure of 50 to 400 pounds per square inch.
5. The process for the manufacture of l-nitrocyclohexene which comprises reacting cyclohexene and nitric oxide in the presence of acetic anhydride, in the absence of air, at temperatures between 90 and 125 C., and at a pressure from 50 to 400 pounds per square inch.
6. The process for the preparation of 1-nitrocyclohexene which comprises reacting cyclohexene and nitric oxide in the presence of acetic acid in the absence of air at temperatures between 90 and 125 C. and at pressures from .50 to 400 pounds per square inch.
'7. The process for the preparation of omeganitrostyrene which comprises reacting styrene and nitric oxide in the presence of acetic anhydride, in the absence of air, at temperatures between 90 and 125 C. and at a pressure from 50 to 400 pounds per square'inch.
RICHARD EDWARD BENSON.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,314,615 Franklin et al Mar. 23, 1943 2,542,935 Bond Feb. 27, 1951 OTHER REFERENCES Groggins, Unit Processes in Organic Synthesis, page 1, Final edition (1947), McGraw- Hill Book 00., Inc.

Claims (1)

1. THE PROCESS FOR THE PREPARATION OF A NITROOLEFIN WHICH COMPRISES REACTING WITH NITRIC OXIDE AND OLEFIN CONTAINING MORE THAN TWO CARBON ATOMS, SAID REACTION BEING CONDUCTED IN AN ACID MEDIUM IN THE ABSENCE OF AIR AT TEMPERATURE FROM 80 TO 150* C. AND UNDER PRESSURE OF 50 TO 400 POUNDS PER SQUARE INCH.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2867669A (en) * 1954-08-19 1959-01-06 Gen Electric Method of forming mononitro hydrocarbons
US3240823A (en) * 1965-04-08 1966-03-15 Atlantic Refining Co Preparation of nitroolefins
US3847801A (en) * 1972-12-27 1974-11-12 Exxon Research Engineering Co Process for separating hydrocarbon
US3894141A (en) * 1972-12-27 1975-07-08 Exxon Research Engineering Co Process for removing nitric oxide
US4642396A (en) * 1984-08-07 1987-02-10 Air Products And Chemicals, Inc. Process for separating nitroaromatic compounds from spent nitric acid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2314615A (en) * 1939-07-25 1943-03-23 Ici Ltd Production of nitro compounds
US2542985A (en) * 1947-01-31 1951-02-27 Houdry Process Corp Preparation of acetophenone from alpha-methyl styrene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2314615A (en) * 1939-07-25 1943-03-23 Ici Ltd Production of nitro compounds
US2542985A (en) * 1947-01-31 1951-02-27 Houdry Process Corp Preparation of acetophenone from alpha-methyl styrene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2867669A (en) * 1954-08-19 1959-01-06 Gen Electric Method of forming mononitro hydrocarbons
US3240823A (en) * 1965-04-08 1966-03-15 Atlantic Refining Co Preparation of nitroolefins
US3847801A (en) * 1972-12-27 1974-11-12 Exxon Research Engineering Co Process for separating hydrocarbon
US3894141A (en) * 1972-12-27 1975-07-08 Exxon Research Engineering Co Process for removing nitric oxide
US4642396A (en) * 1984-08-07 1987-02-10 Air Products And Chemicals, Inc. Process for separating nitroaromatic compounds from spent nitric acid

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